CN101783413A - Manufacturing method of electrochemical battery cell - Google Patents

Manufacturing method of electrochemical battery cell Download PDF

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Publication number
CN101783413A
CN101783413A CN200910253225A CN200910253225A CN101783413A CN 101783413 A CN101783413 A CN 101783413A CN 200910253225 A CN200910253225 A CN 200910253225A CN 200910253225 A CN200910253225 A CN 200910253225A CN 101783413 A CN101783413 A CN 101783413A
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electrode
battery
electrolyte
metal
positive electrode
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冈瑟·汉比特泽
L·津克
H·比奥泽
M·博克
C·里普
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
    • H01M50/618—Pressure control
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Abstract

The invention relates to an electrochemical battery cell with a negative electrode, an electrolyte containing a conducting salt, and with a positive electrode. The electrolyte is based on SO2, and the space between the positive electrode and the negative electrode is formed in such a manner that when the cell is being charged, the active material deposited on the negative electrode can come into contact with the positive electrode such that locally limited short-circuit reactions occur on the surface thereof.

Description

The manufacture method of electrochemical cell
The application is that application number is 200480027573.8, the applying date is 2004.09.21, denomination of invention is divided an application for the application for a patent for invention of " electrochemical cell ".
Technical field
The present invention relates to a kind of electrochemical cell, it has negative electrode (negative electrode), the electrolyte that comprises conducting salt and positive electrode (anode).The present invention especially refers to alkali metal battery, and wherein active material is an alkali metal, and to battery charge the time, described alkali metal is stored in the negative electrode and/or on the negative electrode.But active material also can be second group a metal of other metals, especially alkaline-earth metal or periodic system.Electrolytical conducting salt is made up of metal cation that forms active material and the anion that matches.In the situation of alkali metal battery, alkali-metal four aluminum halide hydrochlorates (LiAlCl for example 4) preferably be used as conducting salt.
Background technology
For example following main reference alkali metal battery, especially lithium battery.Yet this should not be understood that it is restriction to general applicability of the present invention.
Be typically a kind ofly by a plurality of structure of forming of layer of piling up for this battery, described layer area size is than big many of its thickness.They have the area size of same size, and are arranged by stacked on top ground in the interlayer mode in battery.Have the prismatic battery of the shell that is generally rectangular-shaped and straight layer and within it each layer of portion for cylindrical plate around cylindrical battery be common.
Common battery has at least three layers, also is negative electrode, positive electrode and spacer, and it is two electrodes separately on electric and mechanically.This spacer must solve a following difficult problem:
-it should guarantee that the electricity of positive electrode and negative electrode separates, under the situation that electricity separates, battery can not move.
-it should help to guarantee the even distribution of liquid electrolyte between electrode.
-it should guarantee the mechanical separation of anode chamber and cathode chamber, but not only should guarantee needed electrolyte conveying on the other hand but also should guarantee gas delivery between two seed cells of battery.
-it should prevent the short circuit between the electrode reliably.At this,, then produce specific question if reactive metal is deposited to the surface of electrode to battery charge the time.
If active material especially is not to be deposited as the smooth layer with flat surfaces after a plurality of chargings and discharge cycles, but is deposited with the part linear shape, the problems referred to above are especially serious so.Under alkali metal battery, especially lithium battery situation, to battery charge the time, form the line of the not bifurcated with (for the particular battery with particular electrolyte) basic identical diameter especially, the mixed and disorderly growth of described line is agglomerating, and is known as palpus.Must formation owing to because self discharge reaction and on the reactive activity metal surface, forming and not exclusively uniformly thin cover layer.Therefore, the reactive metal of electrolytic deposition is preferably grown on thinner position and is passed cover layer, and distinguishes online terminal continued growth then.
Because form this wire shape, spacer is mechanically seriously stressed.On the other hand, suitably the selection of material requires restriction by other:
-spacer material must be inertia in battery;
-it must be thin as far as possible, so that can realize high-energy-density;
-in addition, the performance data of battery and its useful life are determined jointly by the permeability of spacer for electrolytic ion in addition;
The cost of-spacer must bear.
The spacer that ideally works is a particular importance in lithium ion battery and lithium polymer battery.If the lithium metal is deposited on the surface of negative electrode there, the high response metal can contact with positive electrode in no instance so, because can be caused being called as the uncontrolled reaction result of " thermal runaway " immediately by the caused short circuit of this contact.The organic electrolyte of this battery will burn or even blast uncontrollably.Because these risks are general only with the described battery types of quite little scale manufacturing.In addition, taking that add, primary is the safety measure of electronics.
In described battery types, negative electrode is constituted as usually so-called " insertion electrode ".This notion represents that generally promptly described electrode portion so within it comprises reactive metal with bottom electrode, makes to exchange with electrolyte with regard to preparing to battery charge and discharge the time.In lithium ion battery and lithium polymer battery, negative electrode is based on the insertion electrode of graphite, portion within it, and to battery charge the time, the metal ion of conducting salt is absorbed.If possible, should so move battery, the feasible running status of avoiding reactive metal on electrode surface, to deposit.But this only can utilize actually and expend huge electronics measure and realize, avoids overcharging of battery reliably and with the current strength charging of quite high (surpassing the limiting value that is applicable to each battery) by described electronics measure.This electronic system must clock like precision, and (open circuit voltage for example is 4.2V ± 0.01V) and extremely reliable (per 100,000,000 occur a mistake at most).Increased cost greatly by this measure.Yet, still have certain risk.
Summary of the invention
In view of the above, task of the present invention is, but provide a kind of electrochemical cell of recharge, especially alkali metal battery and primary be lithium battery, with the least possible high as far as possible safety standard of realization that expends, wherein the advantageous feature of each battery types (under the lithium battery situation especially its unsurpassed high-energy-density) should keep fully or even should further be improved by it.
According to the of the present invention first main aspect, this task is by having negative electrode, comprising the electrolyte of conducting salt and the electrochemical cell of positive electrode solves, and wherein electrolyte is with SO 2Be the basis, and the medial compartment between positive electrode and negative electrode constituted so, make when to battery charge, the active material that is deposited on the negative electrode may contact with positive electrode like this, and the short-circuit reaction of local restricted system consequently takes place in its surface.
In scope of the present invention, be determined by experiment, contact with positive electrode if be deposited on the lip-deep reactive metal of negative electrode, so at its electrolyte based on SO 2Battery in, can observe complete undesirable short circuit characteristic.If make by adequate measures this short circuit local restricted system then neither to cause " thermal runaway " in the reaction that this occurred, do not make yet reactive metal a part of passivation and reduce the irreversible reaction of battery charge capacity thus.Or rather, determine, will never negatively influence the characteristic of battery by the short circuit of this local restricted system and relevant with it reaction according to experiment.Therefore, battery of the present invention is worked under the situation of spacer not having.Replace, this battery is so constituted, and makes the active material that on purpose allows to be deposited on negative electrode to battery charge the time contact partly with positive electrode.This expression deviates from basically in common so far battery structure.
As described, this observation is applicable to that its electrolyte is based on SO 2Battery.Electrolyte is called as and " is based on SO 2", described electrolyte not only comprises SO with minimum concentration as additives 2, and moving of the ion of wherein that comprised in electrolyte and conducting salt that cause charge transport passed through SO at least in part 2Guarantee.To this, other information can draw from WO 00/79631 and the document of wherein being quoted.
According to the present invention based on experiment, partial short-circuit and relevant with it electrolyte variable conductance heat activation metal and SO 2The formation of compound, under the situation of lithium battery, caused hydrosulfurous acid lithium (Li 2S 2O 4) formation.Although this compound is difficult to dissolving, there are not a kind of initial product that in reaction, is consumed (Li and SO 2) can from battery functi on, be retracted constantly, because the formation of dithionite and decomposition reaction oppose, this decomposition reaction must be enough to realize the balance favourable to battery functi on soon.To this, can from WO 00/79631, know more detailed description.
In addition, in the zone of partial short-circuit, the reaction with positive electrode may take place.This is particularly useful for following battery, and in described battery, positive electrode comprises metal oxide, especially comprises the oxide that atomic number is 22 to 28 transition metal.This oxide is preferably as the intercalation compound of one of reactive metal, described transition metal and oxygen.In described metal, especially preferred is cobalt, nickel, iron.Comprise the binary of two kinds or three kinds different transition metal and the intercalation compound of ternary metal oxide especially also has practical significance with lattice structure.With regard to particularly preferred this electrode material in the present invention, also can replenish with reference to WO 00/79631 and with reference to the United States Patent (USP) of being quoted there 4,567,031.According to inventor's understanding, for example when the positive electrode that uses based on cobalt oxide, owing to following reaction takes place partial short-circuit:
CoO 2+Li→LiCoO 2。
This reaction is corresponding to the intercalation of reactive metal to battery discharge the time.
When two kinds of running statuses, lithium metal at first so is deposited on the negative electrode, feasible if there is no spacer, so because when charging or when overcharging with extra high current strength, if the quantity of electric charge of being carried when also promptly charging surpasses the capacity of negative electrode, lithium metal just may contact with positive electrode.In these running statuses, not only there is not harm corresponding to the short-circuit reaction of battery discharge, and also or even it is favourable.Therefore, partial short-circuit even play a part favourablely and can be called as " favourable short circuit ".
In a word, in the experimental test of the present invention, determined, utilized the battery of no spacer, be aspect fail safe, or all obtaining extraordinary result aspect the battery data (cyclical stability, capacity or the like).
In addition, obtain following advantage:
-because there is not the spacer that has very thin hole and be easy to stop up pore, so the internal resistance of battery is reduced.
-because the risk relevant with the spacer damage in the conventional batteries do not exist, so fail safe is enhanced basically.
-because spacer material commonly used shows as very big cost factor, so cost is lowered.
The weight and volume of-battery is reduced, therefore the energy density and the power density that can obtain to improve.
-because depositing relevant risk with reactive metal on battery surface is eliminated, so thereby battery can and be recharged apace with very high current strength.
-can use the common production equipment that for example is used for lithium ion battery.
Be necessary to guarantee by adequate measures, short circuit be local restricted system by the relevant reaction of the caused heating of short circuit.
In order to realize this target, be provided preferably with the porous separator, it so is arranged and constitutes, make when the time to battery charge, the active material that is deposited on the negative electrode can grow pass separator hole till the surface of positive electrode.The porous separator preferably directly contacts with positive electrode, and wherein both surfaces contact all sidedly.
The hole of separator must must be enough to it greatly and allow active material undesirably to grow into the surface of positive electrode.Simultaneously, structure and layout with respect to positive electrode must so be designed, make that be restricted on the local part scope of the contact between active material and the positive electrode at electrode surface, therefore partial short-circuit only takes place, and this partial short-circuit does not cause the reaction of other lithiums (its be arranged in the porous separator or on other parts at the interface of itself and negative electrode).If partial short-circuit will trigger other short circuits, then must reckon with the uncontrolled dissipation of lithium, also be " thermal runaway " because violent temperature rises.
Must determine porous insulation layer structure suitable in single situation individually at each battery structure.At this, what consider is that battery ground of battery of diameter of formed palpus has nothing in common with each other when lithium deposits.When being compared, the battery with different electrolyte work shown this point especially clearly.With using based on SO 2Electrolyte the time compare, described must have bigger diameter usually when using organic bath.Therefore, possible fully is in first battery structure, have the growth that specific porous layer prevents palpus, and therefore serve as spacer, and in another battery, identical layer to be infiltrated by the active material that is deposited.
For this reason, in fact can not provide numerical value or other quantitative explanations about the aperture of suitable separator.In addition, because pore-size distribution is significant, so under present case, can not use frequently-used data to characterize suitable layer material such as the manufacturer of the porous layer material of " average pore size " and " maximum diameter of hole ".For example, may be suitable yet the superfine fine pore with high percentage also has the layer of the thick hole of sufficient amount, wherein active material can be grown and be passed this thick hole.Yet, as following will further describing, can no problem ground detect the suitability of the layer material that is used to satisfy function described here according to test.
The porous separator for example can be constituted as the self-supporting film, utilize the porous composite construction of being made up of particle, fiber or microtubule section of adhesive, perhaps also can be constituted as loose charging.If use layer fully well, make electrolyte infiltrate this layer easily, then under any circumstance all be favourable.Preferably, the porous separator comprises the pore structure material of particle shape, fibrous or tubulose, and it especially can be formed by oxide, carbide or chemically stable silicate.The terpolymer of being made up of tetrafluoroethene, hexafluoropropylene and vinylidene fluoride is particularly suitable as adhesive.
The porous separator is unnecessary be can with other functional layers of battery layer of separating of distinguishing.This is particularly useful for the preferred form of implementation of the present invention, in this form of implementation, negative electrode for example comprises the planar substrate and the nonconducting sedimentary deposit that links to each other with this substrate with the conduction electron of thin plate, foam or the form of fabric that is made of metal, this sedimentary deposit is so constituted and is arranged, the active material that makes on substrate surface to be deposited immerses in its hole, and continues there to be deposited.This structure basis WO 02/09213 of institute's reference in this respect is known.Yet, compare with described battery structure there, according to the present invention, between sedimentary deposit and positive electrode, do not exist the impervious barrier layer of active material.The favourable porous separator of localization to the short circuit that occurred inevitably owing to lack the barrier layer can be (can not divide) whole part of sedimentary deposit, perhaps can form by the layer that separates, the layer of this separation and should and be to combine all sidedly with the seamless unoccupied place of sedimentary deposit between sedimentary deposit and positive electrode.
Usually, the present invention is proved to be particularly advantageous in this battery structure, and wherein negative electrode so is configured in this battery structure, makes that the positive metal ion of conducting salt is absorbed into its inside to battery charge the time.In this structure, when battery was charged normal, the deposition of reactive metal on electrode surface at first do not take place, but the storage of the reactive metal when in the inside that is the structure of negative electrode part charging process taking place.The battery types that these conditions were suitable for is commonly called " insertion electrode " here.The previous constructions of the sedimentary deposit that has the planar substrate of conduction electron and be attached thereto also can be counted as the insertion electrode on the common meaning, and wherein active material is absorbed in the hole of described sedimentary deposit when charging.
According to another flexible program, positive metal ion is absorbed into the inside of conductive electrode material of the part that is negative electrode.The important example of this conductive electrode material is as the carbon-containing electrode that also is used to lithium ion battery, especially graphite electrode.At this, when charging, the storage of lithium is not by the deposition in the porous cavity but is undertaken by the intercalation in the lattice structure of conductive electrode material.Except above-mentioned graphite electrode, based on Li 4Ti 5O 12Lithium intercalation electrode or alloy electrode can be used as the kind electrode examples of material.
In this battery structure, definitely be necessary to exist the porous separator of separation, thereby so that prevent from directly to electrically contact and prevent short circuit between negative electrode and the positive electrode (also being its electrode substance that conducts electricity respectively).Also to further describe this design with reference to the accompanying drawings below.
The second main aspect relates to the manufacture method that is used for electrochemical cell, the purifying step that especially takes place in this method inside, wherein, and by removing the OH of chemical combination on electrode -Ion comes at its function optimization battery electrode.This method is particularly useful for making according to the described battery in the of the present invention first main aspect, but also has independently meaning.
According to the second main aspect, remove OH from electrode -Ion wherein makes to comprise and OH -First cleanser that purifies composition of ionic reaction so contacts with electrode, makes by coming to remove the OH of institute's chemical combination thereon from electrode surface with first reaction that purifies composition -Ion, and get on except that the part of cleanser or may disturb the product of battery functi on from electrode.
For non-aqueous battery, also promptly especially utilize based on SO 2The function of battery of electrolyte work extremely important be that the residual water that exists in electrode structure (not only refers to molecular water but also refers to H +Ion and OH -Ion) is removed fully.This is a difficult problem when using prior described insertion electrode especially.
Determine that in the scope of the invention existence of the water of chemical combination may cause the passivation of electrode, makes electrode process to carry out with delaying.Under the situation of inserting electrode, especially (for example metal oxide intercalation compound of known above-mentioned other types from WO 00/79631) alkali metal intercalation electrode, this relates to alkali-metal shifting out or the insertion when discharge to battery charge the time.Passivation causes the increase of the internal resistance of cell.
Discovery according to the inventor, passivation can owing to, the reaction of the surface molecular of electrode and water (for example come from there was dampness in the air) causes tectal formation, and this cover layer comprises the hydroxide of reactive metal, also promptly comprises the compound of AOH type under the situation of alkali metal A.Even the water of trace all can cause the tectal formation of hydroxide.According to inventor's understanding, when making electrode, just almost can not avoid tectal formation, the active material of wherein said electrode is with metal oxide intercalation compound, especially LiCoO 2For the basis.This not only relates to the outer surface of electrode, and (under the common situation of porous electrode material) also relates to (in hole) inner surface.The passivation of electrode can be by eliminating described purification composition and OH with the reaction that purifies composition -Ionic reaction and be called as first here and purify composition.Under situation about being without loss of generality, this first purification composition is also referred to as activating component hereinafter.
The theme of the present invention's second major part also is to insert electrode, especially its surface not have OH basically -The intercalation electrode of ion.Preferably, electrode does not have H basically yet +Ion.The electrochemical cell that comprises kind electrode also is a theme of the present invention.At this, " do not have OH basically -Ion or H +Ion " can be understood as: electrode passivation relevant with the existence of ion or caused capacity loss are not to exist with degree like this so that influence electrode actual functional capability in the battery.As following also will be in greater detail, passivation causes that the internal resistance of cell constantly increases when charging and discharge cycles.Equally as following also will be in greater detail, relevant therewith electrode characteristic for example can be investigated by means of cyclic voltammogram.Preferably, the active material surface does not have hydroxyl ion and is cleaned into by means of first by preceding method and assigns to realize.
Determined that in the scope of the invention insertion electrode of type discussed herein has the content of water of chemical combination of the 10000ppm order of magnitude (also promptly with respect to electrochemical activity electrode material, especially LiCoO 2Be the H of 1% percentage by weight 2O).The electrode of optimization of the present invention have water content be up to 5000ppm, preferably be up to 1000ppm, especially preferably be up to 100ppm and extremely preferably be up to 10ppm.
The Lewis acid of no proton has been proved to be the first especially suitable purification composition.This notion refer on the meaning of the definition that G.N.Lewis provides, have acidity (that is to say electron acceptor), but do not comprise H +The material of ion.The preferred example of Lewis acid is AlF 3, BF 3, CO 2, CS 2And GaCl 3Usually can test the suitability of Lewis acid according to experiment for the object of the invention.
The preliminary election of suitable Lewis acid can be carried out based on its intensity, and its intensity again can be from forming sour atom (at AlF 3Situation under for example be Al and F) the difference of electronegativity value estimate.This difference is big more, and Lewis acid is strong more.
Cleanser is liquid normally, and it comprises this first composition in appropriate solvent.As solvent, aprotic liquid, for example carbon tetrachloride (CCl 4) especially be fit to.The necessary no water-based of solvent can be for example by means of molecular sieve, especially realize based on metallic aluminium silicate with big surface.In principle, especially based on supercritical CO 2Gas or supercritical liq also can be used as solvent.Purify composition self even also can be with liquid (supercritical CO for example 2) or gas (CS for example 2) exist.In these cases, cleanser needn't comprise additional solvent certainly.
The concentration of activating component should be high as far as possible in cleanser, wherein under the situation of solution, draws the upper limit from the solubility of activating component.Usually, saturated solution is preferred.But activation also is possible in principle when pettiness concentration.Under single situation, suitable concentration must be determined with the mode of experiment in conjunction with the duration of purified treatment, and also depend on employed Lewis acid certainly.
Cleanser must satisfy following condition in practice:
-as long as apply this method like this, make at least a portion cleanser when making battery, be retained in and insert in the electrode that so thus, cleanser must be harmless to battery functi on.Harmful part must be able to be removed easily and fully.
-cleanser must be compatible with electrode material.Especially do not allow to cause the reaction of disturbing its function.
According to preferred form of implementation, in manufacture method, second purifies composition is used to optimize the insertion electrode, this second purification composition and H +Ionic reaction, and so contacting with inserting electrode in cleanser makes the H of in described electrode institute's chemical combination +Ion is by dissolving from the inside of electrode with second reaction that purifies composition.Determined within the scope of the invention, inserted electrode, especially the intercalation characteristic of electrode of the above-mentioned type is also because H +Ion (proton) chemical combination is to electrode material and undermined.This proton and the alkali metal ion exchange of inserting electrode reduce its absorbability to reactive metal (especially alkali metal) thus, thereby and reduce battery capacity.By means of the second purification composition, proton is separated out from insert electrode.Thereby improved its absorptive capacity thus and improved the electric memory capacity of battery.
Especially salt is suitable as second and purifies composition, and described salt carries out ion-exchange reactions with the proton of institute's chemical combination in inserting electrode.Suitable examples is halide, the especially fluoride of the metal of alkali metal, alkaline-earth metal or periodic system the 3rd main group.Under situation about being without loss of generality, " purification salt " hereinafter also is used to second and purifies composition.
Purify compositions and its with regard to the application in the manufacture method with regard to two kinds, different flexible programs is possible.For example when making electrode substance, just can be being incorporated in this electrode substance to the small part amount of purification salt, thus and be incorporated in the electrode.Also can use the method that wherein directly first the and/or second purification composition is not incorporated in the cleanser.Or rather, also there is the possibility that forms these compositions by means of suitable pre-reaction on the spot certainly.Salt, anion PF especially 6 -, AsF 6 -, BF 4 -And AlF 4 -Salt be exemplary, described salt can form purification salt by division halide, preferred fluorinated thing.Organic salt also goes for forming the initial product that purifies salt on the spot as being used for.
According to the advantageous modification of this manufacture method, in two independent step, divide two stage ground to carry out OH -And H +Independently (preferably also being different) solvent is wherein used in the removal of ion respectively.
Especially, in the phase I, the insertion electrode is contacted with cleanser, described cleanser contains Lewis acid, for example CCl that has or not proton in volatile aprotic solvent 4This cleanser is worked always, up to OH -Ion is till electrode is transferred to the cleanser.Remove this cleanser then.
In second stage, electrode is contacted with second cleanser that comprises the second purification composition.Proton being transferred to from electrode after necessary reaction finishes the cleanser, also can remove second cleanser once more.The electrode of the optimization that obtains must be continued to handle in anhydrous atmosphere certainly, so that its characteristic is not by absorbing water and its part OH -And H +And variation once more.
The solvent that also can be used as in principle, scavenging solution for the electrolyte that each battery provided.Especially advantageously, with electrolyte suitable purification salt is introduced in the battery.Because by carry out the compound (for example HF and HCL) that ion-exchange forms with the proton that is comprised in inserting electrode is volatile,, wherein can quicken leakage by adopting negative pressure (finding time) so himself can leak.In this case, scavenging solution needn't be removed from battery, but stays in the battery as electrolyte, wherein purifies positive role that remainder that salt stays has other (except separate out H from electrode +Outside the ion).
In principle, both can also can utilize cleanser to handle electrode at inside battery at outside batteries.Under the situation of dual stage process, can especially advantageously carry out for the first method stage at outside batteries and (remove OH -Ion), the electrode that the part of packing in battery is then optimized, and in battery, carry out second cleansing phase (separating out the H+ ion).
The present invention the 3rd main aspect relates to the filling of battery electrolytic solution.The method and apparatus that is used to fill electrochemical cell has been described in DE 19911800C1, its for example should be used to solve with based on SO 2The relevant specific question of electrolyte.This electrolyte is the salt of solvation, its solvent (SO 2) when room temperature, be gaseous state.In order to overcome relevant with it specific question, advise a kind of complicated apparatus, its middle sleeve must pass battery inlet airtightly and be introduced to electrode and pile up.Thus, exist following dangerously, promptly the tube ends lesion electrode piles up and causes internal short-circuit.In addition, the conducting salt that can be easily be separated out by crystallization of this thin sleeve pipe stops up.In order to fill, battery is evacuated, and after conversion valve, electrolyte is inhaled in the battery.At this, big pressure reduction is disadvantageous between electrolyte and the inside battery.During beginning, solvent (SO 2) from electrolyte, be evaporated.Thus, the danger that danger that the conducting salt crystallization separates out and filling device are stopped up increases.
In contrast, in the scope of the invention, advise a kind of simpler method, it preferably is used in conjunction with two other main aspects, but also can have independent meaning.At this, the injection of electrolyte comprises step by step following:
The inner room of-shell gaseous state SO 2Fill;
The inlet of-shell is connected on the container airtightly, and this container comprises and has a part of SO 2Electrolyte, wherein so limit described a part of SO 2, make gaseous state SO 2Promptly be dissolved in the electrolyte; With
-by driving, electrolyte is flowed in the shell by the negative pressure that course of dissolution caused.
Also to provide more detailed description below based on accompanying drawing.This method can make battery use based on SO simply 2Electrolyte fill up fully.
According to the 4th main aspect, the present invention handles a problem, and this problem is drawn by following, promptly especially has based on SO 2Electrolytical battery in, when battery is charged for the first time, on negative electrode, form cover layer based on the electrochemistry situation.Determine that in the scope of the invention reason that the discharge capacity of battery significantly reduces is that this cover layer forms, and can be by realizing relevant therewith optimization the needed reactive metal of formation cover layer is transferred to one of electrode from replenishing one's stock, wherein
-replenishing one's stock contacts with electrolyte,
-auxiliary electrode contacts with the electrolyte conduction,
-at auxiliary electrode and should transfer to reactive metal set up between the electrode on it that electric line connects and
-transfer at auxiliary electrode with reactive metal to flow between the electrode on it by electric current and cause the transfer of reactive metal.
Under situation about being without loss of generality, be that alkali-metal battery is described this main aspect also below according to its reactive metal.At this, cover layer is by alkali metal dithionite (A 2S 2O 4) form, also promptly under the situation of lithium battery by Li 2S 2O 4Form.Form cover layer based on electrochemical conditions, wherein can followingly describe described electrochemical conditions simply, promptly at voltage (under the situation of Li battery to Li/Li +Since 3 volts) tectal reaction just taken place to cause forming when being lower than the normal working voltage of battery.Therefore, thus metallic alkali metal be stored on the negative electrode or be stored in the negative electrode and rechargeable battery before, at first preferably form dithionite.
Be used to form Li 2S 2O 4(also exemplary described here) lithium at otheralkali metal usually from positive electrode.This causes, and when first charging cycle, the part to the necessary lithium of battery capacity is consumed originally.If the active material of negative electrode is a porous extremely, and therefore has big inner surface, then this problem especially severe.Produce corresponding big coverage rate thus, and in charging process at first, be consumed, to form cover layer in the major part (for example about 25%) of the lithium that begins in positive electrode, to be comprised before the charging process.If negative electrode is mainly based on the insertion electrode of graphite, then this problem especially exists.
The difference of the different forms of implementation of the 4th main aspect just is source, the employed auxiliary electrode of the reactive metal that adds and is the electrode that the diverts the aim aspects such as (hereinafter being " target electrode ") of additional activity metal.
Replenishing one's stock of reactive metal especially can be used in the following flexible program, and described flexible program also can be used in principle with being bonded to each other:
-can be used as pure (also promptly non-chemically chemical combination) metal (preferably by immersing) reactive metal is contacted with electrolyte.
-can the container outside battery case in or in battery self, prepare the electrolyte of additional quantity.Under former instance, additional electrolyte is connected with electrolyte in the battery via (can realize ion carry) electrolyte bridge.
-additional reactive metal can with suitable compound, under the situation of alkali metal A preferably as its dithionite A 2S 2O 4Form be used.
In principle, auxiliary electrode can be made of conducting element, and this conducting element is together with the necessary parts of operation battery are immersed in the electrolyte.Yet, preferably the shell of battery self, at least one current-carrying part of its inwall is used as auxiliary electrode or rather.If the source of additional metal is a metallicity conduction, then this is derived from body and also can constitutes auxiliary electrode.
Target electrode both can be the negative electrode of battery, also can be positive electrode.
-should be after injecting electrolyte, but the transfer of reactive metal from the negative electrode that replenishes one's stock took place before battery is charged for the first time, and continue always, heretofore on the surface of electrode with approximately when battery is charged normal identical amount formation cover layer (metallicity alkali metal be stored on the negative electrode or before in negative electrode) till.
-under the situation of positive electrode, relate to by alkali-metal accessory supplied and compensate the loss that the result occurred that in positive electrode, forms in front the charging process as cover layer.In this case, after injecting electrolyte, by battery charge is formed cover layer on negative electrode, wherein this charging process should preferably be proceeded always, thus up to metallicity alkali metal be stored on the negative electrode or in negative electrode and rechargeable battery till.After this, to positive electrode supply reactive metal, thus and the compensation alkali metal of in charging process, being separated out.
Description of drawings
Below, the present invention is described with reference to the accompanying drawings in more detail.For the present invention is provided preferred improvement project, shown in can using either alone or in combination and described characteristics.
Fig. 1 illustrates the schematic cross-section by battery of the present invention;
Fig. 2 illustrates the perspective schematic diagram of the layout and the dimension scale that are used for illustrating in embodiments of the present invention electrode substance;
Fig. 3 illustrates and is used to illustrate the perspective schematic diagram of selecting the method for suitable material according to experiment for the porous separator;
Fig. 4 illustrates the diagram according to the measurement result of experiment test of the present invention first main aspect;
Fig. 5 and Fig. 6 illustrate the cyclic voltammogram according to experiment test of the present invention second main aspect;
Fig. 7 illustrates based on the summary figure according to Fig. 5 and 6 results' that obtained cyclic voltammogram;
Fig. 8 illustrates the curve chart of the discharge capacity of the cell that depends on charging and discharge cycles number of times;
Fig. 9 illustrates the schematic diagram that is used to illustrate the present invention the 3rd main aspect;
Figure 10 illustrates the schematic diagram of first flexible program that is used to illustrate the present invention the 4th main aspect,
Figure 11 illustrates the schematic diagram of second flexible program that is used to illustrate the present invention the 4th main aspect;
Figure 12 illustrates the part schematic diagram of the 3rd flexible program that is used to illustrate the present invention the 4th main aspect.
Embodiment
The schematically illustrated electrochemical cell 1 with shell 2 of Fig. 1, the interlayer that has layer at inside battery is arranged, also is negative electrode 3, porous separator 4 and positive electrode 5. Electrode 3,5 links to each other with connecting terminal 8,9 via electric conductor 6,7, and in order to charge, battery can link to each other with charging device by this connecting terminal, perhaps links to each other with customer in use.
Being configured in of battery is conventional to a great extent, needn't further specify.An important characteristic is, do not have spacer between electrode 3,5, but has porous separator 4, and this porous separator helps to pass this separator 4 in the reactive metal growth that is deposited on the negative electrode surface of positive electrode 5 to battery charge the time.At this, contact in the part that between the surface of negative electrode 3, occurs of reactive metal and positive electrode 5, and therefore partial short-circuit takes place.
Fig. 1 illustrates and Fig. 2 clearly show that, electrode 3,5 is preferably much thick than separator 4.Separator 4 preferably has the thickness of maximum 100 μ m, and electrode has the thickness that typically is approximately 0.1mm to 2mm.These numerical value show, though diagram in the drawings is pro rata haply with regard to thickness relationship, are not pro rata with regard to the absolute thickness of layer.Or rather, commercial battery generally comprises the bag of being made up of a plurality of thin layers.Except characteristics described here, thus, the present invention and common battery are as broad as long.
The relative big thickness with 5 of electrode 3 is associated with following, promptly shown in preferred implementing form in, two electrodes have conductive electrode material 11 or 12, wherein to battery charge or when discharge, the ion of reactive metal is absorbed in the described conductive electrode material.Suitable material is above referred.Particularly preferably, negative electrode 3 is graphite electrodes, and wherein its (preferably porous) electrode substance 11 is made up of carbon to a great extent.Positive electrode is the intercalation electrode preferably, and its electrode substance 12 is made of cobalt acid lithium, and preferably has loose structure equally.In discharge condition, lithium is stored in positive electrode inside.When charging, lithium ion moves in the electrode substance 11 of negative electrode by porous separator 4.In the running status of determining, as mentioned above, the deposition of reactive metal on the interface between electrode substance 11 and the porous separator 4 takes place also in addition.At this, reactive metal infiltrates in the hole of separator 4, and growth passes porous separator 4, till on the interface between positive electrode 5 and the separator 4, described partial short-circuit takes place on this interface at last.
In Fig. 1 and 2, be not illustrated in needed electrical connection between electrode substance 11,12 and the electric conductor 6,7.This electrical connection is by can guaranteeing with the metallic conductor element that electrode substance 11,12 is connected usually.For example can use the lip-deep thin conductor sheet that deviates from porous separator 4 in electrode substance 11 and 12, but also can use the porous metal structure such as the foaming metal form, wherein electrode substance is incorporated in this porous metal structure some or all ofly.Just in this point, because this structure is known according to prior art, so also do not need to describe in detail.
As above described like that, the structural feature of porous separator 4 can not be described with common binding value (for example about porousness and structure part), wherein obtain needed within the scope of the present invention characteristic (to the permeability of the active material that on negative electrode, deposited, and the short circuit of the local restricted system of assurance) by described structural feature.But can test the material that provides for separator suitability simply to particular battery according to experiment.In Fig. 3, show suitable experiment structure in mode extremely schematically.This experiment structure is made up of following sequence:
By the metal negative electrode 15 of nickel; The metal film of making by nickel and all be fit to by foaming metal or draw metal that nickel is made.
Test material 16: test its material to the suitability of separator 4.
By the metal auxiliary electrode 17 of nickel; It must be that liquid is porous and may for example be made up of the plate of draw metal or punching.
Spacer 18: common isolated material is fit to; In this experiment structure,, only depend on its electrical insulation characteristics being permeable while to electrolyte.
Positive electrode 19: the LiCoO in the foaming nickel 2
Layer is by stacked on top, and is and compressed together by means of a framework that does not illustrate.Total is immersed in based on SO 2Electrolyte in, the component of this electrolyte is corresponding to the electrolyte of the battery of being planned.
Shown Experimental cell charges by means of charging device 20, wherein (as in advance at the battery of Fig. 1 and 2 described) lithium separates out from positive electrode 19, and deposits in the negative electrode.In discharge process, by means of the electrical potential difference of voltage measuring apparatus 21 monitoring between negative electrode and auxiliary electrode.This electrical potential difference is generally 3.3 volts (voltages of Li-Ni-element).If the lithium growth is passed separator 16 up to auxiliary electrode 17, then this causes electrical potential difference to descend.At this constantly, measurement is terminated, and Experimental cell is disassembled.By separator (in the side towards auxiliary electrode 17) is carried out optical detection, can determine the mode of lithium growth.Can discern the position of lithium growth and may accumulating of lithium well.Therefore can determine whether the layer 16 that will detect is permeated in as desired the position in local restricted system to lithium, and therefore is suitable as porous separator of the present invention.
Fig. 4 illustrates the experiment test that the present invention does not have the measurement battery of spacer.Under concrete condition, battery comprises by LiCoO 2Positive electrode of forming and lithium metal directly are deposited on the negative electrode in the loose structure of being made up of carborundum, and described loose structure directly contacts with the electrode substance of positive electrode.LiAlC1 4* 1.5SO 2Be used as electrolyte.
Drawn the capacity C of battery with nominal capacity percentage with respect to the times N of charging and discharge cycles.After producing the initial capacity loss owing to the structure of negative electrode is inhomogeneous, volumetricization is to 90%.This represents the high-effect of no spacer configurations.
The result that Fig. 5 to 8 is drawn when being illustrated in according to the main aspect of experiment test the present invention second.At this, contrasting according to optimised positive electrode of the present invention and not optimised electrode.Test structure has following feature:
Geometric electrode area: 1cm 2
Electrode capacity: 40mAh
Electrolyte: LiAlCl 4* 1.5 SO 2
Electrode material: LICoO 2
Carry out and circulate at common Experimental cell (have and be used for " the E-battery " that the reference electrode of electromotive force is measured on no current ground), in described circulation, between 3.5V and 4.5V, change voltage with the sweep speed of 0.2mV/s.Fig. 5 and 6 illustrates cyclic voltammogram, and at this, this cyclic voltammogram is to utilize not the electrode according to optimization of the present invention to draw on the one hand, is to utilize to draw according to the optimised electrode of the present invention on the other hand.With respect to Li/Li +Half-cell, having drawn with respect to the voltage U that is applied on battery that with V is unit is the measured voltage strength I of unit with mA.Show four circulations respectively, comprising the first circulation Z 1With last circulation Z 40
In the battery with positive electrode of not optimizing by the present invention, Fig. 5 illustrates the clearly variation of cyclic voltammogram, and at first this variation is characterised in that, the position of anode peak value is to bigger variation.This anode peak value also is significantly less than 4V at first circulation time, and when the 40 cycle near 4.2V.This is corresponding to the increase of the internal resistance of cell, and according to inventor's understanding, this increase should be owing to the passivation of positive electrode.
Show in the result shown in Fig. 6, caused cyclic voltammogram in fact not change in 40 cyclic processes according to electrode optimization of the present invention: the electrical value of battery, especially its internal resistance keep constant.
In Fig. 7, show to summing-up these results once more.Here, show peak maximum (U at having according to the optimised electrode of the present invention (curve A) with at having the electrode of not optimizing (curve B) according to the present invention Max(is unit with the volt)) with respect to the variation of cycle-index, wherein carried out in this case more than 150 circulations.This diagram also shows, do not carrying out according to the present invention under the situation that electrode optimizes, and peak changes continuously, thereby and the internal resistance of cell change continuously, and this peak almost keeps constant when using according to the optimised electrode of the present invention.
At having according to the battery (curve A) of the optimised electrode of the present invention and have the battery (curve B) of not optimised electrode, Fig. 8 illustrates the dependence of electric discharge capacity (% with theoretical capacity is a unit) and charging and discharge cycles times N.These characteristic parameters also improve by the present invention basically: on the one hand, it is about 7% that initial capacity has improved, and on the other hand, the capacity relevant with discharge with the recharge of battery descends and diminish basically.
Fig. 9 explanation according to the of the present invention the 3rd main aspect with the filling of electrolyte to battery.At this constantly, electrode and porous separator have been in the shell 2 of battery 1, as shown in exemplary among Fig. 1 like that.This filling process is as follows:
-at first, the shell 2 of battery 1 is evacuated via pipeline 29, and this process can utilize pressure measurement instrument 30 to control.Then, carry gaseous state SO via pipeline 31 2, make and in the inner room of shell 2, use gas SO 2Fill.
-then, the electrolyte of stand-by storage in container 32 is filled.Because the SO of this electrolyte 2Concentration is low, so after the connection of opening between shell 2 and the container 32, the gaseous sulfur dioxide that exists in battery 1 promptly is dissolved in the electrolyte.In other words, the weak exothermic reaction of generation and electrolyte.Thus, the gas flow in the shell 2 is reduced.Negative pressure occurs in battery 1, because this negative pressure, other electrolyte is drawn out of from container 32.At this, electrolyte infiltrates all holes of the layer that is arranged in battery 1 inside.If this time be engraved in the battery conducting salt that there has been the part amount in the result of the purifying step aspect main according to second (for example as), then this also obtains promoting extraly.
Figure 10 to 12 illustrates the of the present invention the 4th main aspect.According to comprising that the battery that lithium as reactive metal, negative graphite insert electrode and has a positive intercalation electrode of the electrode substance of being made up of cobalt acid lithium is described.They can be migrated on the ordinary circumstance of other suitable reactive metals and electrode material easily.
Figure 10 illustrates the battery 2 of filling with electrolyte 24.Can not find out positive electrode in the selected diagram here, existence that still yes.Battery 1 has 25, blocks of lithium metals 26 of the conduit of injection can inject conduit immersion electrolyte 24 by this.Lithium metal 26 is with the negative connecting terminal 8 of battery, also promptly be electrically connected with negative electrode 3.Under the situation that does not apply external voltage, this layout causes lithium 26 to dissolve gradually, and forms the cover layer of being made up of the hydrosulfurous acid lithium simultaneously on negative electrode.In this process, the battery current loop open circuit between negative electrode and positive electrode.
In this form of implementation, lithium metal 26 forms replenishing one's stock of auxiliary electrode and reactive metal simultaneously.On negative electrode NE and auxiliary electrode HE, carry out following reaction:
NE：2Li ++2SO 2+2e -→2Li 2S 2O 4
HE：2Li →2Li ++2e -。
Becoming freely when reacting on auxiliary electrode, electronics is passed to negative electrode 3, the reaction consumes that it is moved there on described negative electrode via circuit connection 27.In this form of implementation, because hot current intelligence does not need voltage source in circuit 27.
In the form of implementation shown in Figure 10, under the situation that does not consume a part of lithium in the positive electrode, before being charged for the first time, battery just on negative electrode, forms cover layer.Therefore, the lithium content of positive electrode can be used for the charging of battery and discharge subsequently fully.
Also can use the layout that is similar to Figure 10, so as by the loss of compensation reactive metal after first time charging process " regeneration " positive electrode once more, wherein in front during charging process because cover layer formation and the described loss of appearance in positive electrode.In this case, positive electrode is the target electrode that lithium shifts, and also promptly after battery is charged for the first time, the circuit between lithium metal 26 and the positive electrode connects 27 and is established, and the battery current loop open circuit between positive electrode and the negative electrode simultaneously.Thus, lithium ion on purpose is inserted in the positive electrode, wherein carries out following reaction there:
PE：Li (1-x)CoO 2+x?Li ++x?e -→LiCoO 2。
Figure 11 illustrates a kind of form of implementation, and wherein the electrolyte 35 of additional quantity is used as replenishing one's stock of lithium.In the illustrated case, electrolytical additional quantity is arranged in container 36, and this container links to each other with electrolyte 24 in the battery 2 via electrolyte bridge 37.Auxiliary electrode 38 connects 39 via circuit and links to each other with the negative connecting terminal 8 of battery, and so links to each other with negative electrode 3.Produce (optimised according to experiment) voltage by the voltage source 40 that connects at circuit among 39 between auxiliary electrode 38 and negative electrode 3, this voltage causes carrying out following reaction on electrode:
NE：2Li ++2SO 2+2e -→2Li 2S 2O 4
HE：2AlCl 4 - →2AlCl 3+Cl 2+2e -。
Reaction on the auxiliary electrode connects 39 via circuit and be provided for producing the needed electronics of cover layer on negative electrode.Needed Li +Ion (also in the conducting salt that is promptly comprised therein) in electrolytical additional quantity is provided use.
Also can use in the layout shown in Figure 11 in the mode that changes, so that the first time charging process with relevant with it lithium consumption after the positive electrode of regenerating, wherein in this case, connect to the circuit of the positive connecting terminal of battery and also to be established, and carry out the transfer of lithium after the charging process in the first time.
Figure 12 illustrates a kind of form of implementation, and in this form of implementation, auxiliary electrode is formed by the wall 42 of the shell 41 of battery 2, and described wall is made up of metal.Therefore, between shell 41 and negative connecting terminal 8, set up circuit and connect 43.Form with hydrosulfurous acid lithium 44 provides replenishing one's stock of lithium, and this hydrosulfurous acid lithium (for example as powder) so is injected in the battery, makes it in the inside and the medial compartment between the negative electrode 3 of shell 41.Thus, below the product of described reaction not only have to the short the evolving path of auxiliary electrode (shell wall 42), and have to the short the evolving path of target electrode (being negative electrode 3 here).
By connect the driven of the voltage source 45 that is access in 43 at circuit, on electrode, carry out following reaction:
NE：2Li ++2SO 2+2e -→2Li 2S 2O 4
HE：2AlCl 4 - →2AlCl 3+Cl 2+2e -。
Reaction on auxiliary electrode (shell wall) causes following other reactions:
(a)：Cl 2+SO 2 →SO 2Cl 2
(b)：SO 2Cl 2+Li 2S 2O 4→2LiCl+3SO 2
(c)：2LiCl+2AlCl 3 →2Li ++2AlCl 4 -。
In reaction (a), the SO on auxiliary electrode in formed chlorine and the electrolyte 2React and form chlorosulfuric acid, it continues reaction and forms lithium chloride and sulfur dioxide with the hydrosulfurous acid lithium that replenishes one's stock as lithium in reaction (b).Based on the product of initial action, reaction (c) causes forming lithium ion, and the cover layer of described lithium ion on negative electrode forms and continue reaction in the reaction.
In this case, positive electrode also can be target electrode, the wherein same similarly situation that is suitable for aforementioned form of implementation.

Claims (8)

1. be used to make the method for electrochemical cell, described electrochemical cell has positive electrode and negative electrode in shell, and this method comprises a method step, in described method step, will have conducting salt based on SO 2Electrolyte inject shell, wherein the injection of electrolyte comprises step by step following:
The inner room of-shell the SO of gaseous state 2Be full of;
The inlet of-shell is connected on the container airtightly, and this container comprises and has a part of SO 2Electrolyte, so limit described a part of SO 2, make gaseous state SO 2Be dissolved in the electrolyte apace; With
-by driving, electrolyte is flowed in the shell by the negative pressure that course of dissolution caused.
2. in accordance with the method for claim 1, wherein said conducting salt is LiAlCl 4, and the SO of electrolyte 2Part is up to LiAlCl 43.5 SO 2
3. in accordance with the method for claim 1, wherein said method combines with following method:
In order to optimize electrode, get on except that hydroxyl ion, wherein from electrode surface
Make to comprise so to contact with described electrode with first cleanser that purifies composition of hydroxyl ion reaction, make since with the reaction of the first purification composition from electrode surface remove institute's chemical combination thereon hydroxyl ion and
From electrode, remove the part of cleanser or may disturb the product of battery functi on.
4. in accordance with the method for claim 1, wherein from the group that the metal of being organized for the second time by alkali metal, alkaline-earth metal and periodic system is formed, select described reactive metal.
5. in accordance with the method for claim 4, it is characterized in that described reactive metal is lithium, sodium, calcium, zinc or aluminium.
6. in accordance with the method for claim 1, wherein said positive electrode comprises metal oxide.
7. in accordance with the method for claim 6, wherein said positive electrode comprises intercalation compound.
8. in accordance with the method for claim 7, wherein said positive electrode comprises and has CoO 2Intercalation compound.
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